WO2010137221A1 - シリカ容器及びその製造方法 - Google Patents

シリカ容器及びその製造方法 Download PDF

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Publication number
WO2010137221A1
WO2010137221A1 PCT/JP2010/002049 JP2010002049W WO2010137221A1 WO 2010137221 A1 WO2010137221 A1 WO 2010137221A1 JP 2010002049 W JP2010002049 W JP 2010002049W WO 2010137221 A1 WO2010137221 A1 WO 2010137221A1
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WIPO (PCT)
Prior art keywords
silica
intermediate layer
molecules
silica container
gas
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PCT/JP2010/002049
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English (en)
French (fr)
Japanese (ja)
Inventor
山形茂
笛吹友美
Original Assignee
信越石英株式会社
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Application filed by 信越石英株式会社 filed Critical 信越石英株式会社
Priority to JP2010540751A priority Critical patent/JP4903288B2/ja
Priority to CN201080016990.8A priority patent/CN102395535B/zh
Priority to EP10780183.9A priority patent/EP2436658A4/en
Priority to US13/055,865 priority patent/US8420192B2/en
Priority to KR1020117026489A priority patent/KR101315684B1/ko
Publication of WO2010137221A1 publication Critical patent/WO2010137221A1/ja
Priority to US13/793,948 priority patent/US8915096B2/en

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/09—Other methods of shaping glass by fusing powdered glass in a shaping mould
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B20/00—Processes specially adapted for the production of quartz or fused silica articles, not otherwise provided for
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/09—Other methods of shaping glass by fusing powdered glass in a shaping mould
    • C03B19/095—Other methods of shaping glass by fusing powdered glass in a shaping mould by centrifuging, e.g. arc discharge in rotating mould
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
    • C30B15/10—Crucibles or containers for supporting the melt
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements
    • C30B29/06—Silicon
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B35/00—Apparatus not otherwise provided for, specially adapted for the growth, production or after-treatment of single crystals or of a homogeneous polycrystalline material with defined structure
    • C30B35/002—Crucibles or containers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
    • Y02P40/57—Improving the yield, e-g- reduction of reject rates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/131—Glass, ceramic, or sintered, fused, fired, or calcined metal oxide or metal carbide containing [e.g., porcelain, brick, cement, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/131—Glass, ceramic, or sintered, fused, fired, or calcined metal oxide or metal carbide containing [e.g., porcelain, brick, cement, etc.]
    • Y10T428/1317—Multilayer [continuous layer]

Definitions

  • the present invention relates to a silica container mainly composed of silica and a method for producing the same, and more particularly to a low-cost, high dimensional accuracy, high durability silica container and a method for producing the same.
  • Silica glass is a lens for projection exposure equipment (lithography equipment) for manufacturing large-scale integrated circuits (LSIs), prisms, photomasks and TFT substrates for displays, tubes for ultraviolet or infrared lamps, windows, reflectors, and cleaning containers for the semiconductor industry. It is used as a silicon semiconductor melting vessel.
  • LSIs large-scale integrated circuits
  • TFT substrates for displays
  • tubes for ultraviolet or infrared lamps windows, reflectors, and cleaning containers for the semiconductor industry.
  • silicon semiconductor melting vessel As a silica glass raw material of such a silica molded body, an expensive compound such as silicon tetrachloride must be used, and the melting temperature and processing temperature of silica glass are as high as about 2000 ° C. For this reason, a large amount of energy is consumed, causing a large amount of carbon dioxide emission, which is considered as one of the global warming gases. Therefore, conventionally, a method for producing silica glass at a relatively low temperature using a relatively inexpensive raw material has been
  • Patent Document 1 discloses a method (sol-gel method) in which silicon alkoxide is hydrolyzed to form a silica sol, then gelled to form a wet gel, dried to a dry gel, and finally a high-temperature calcination to obtain a transparent silica glass body.
  • Patent Document 2 discloses a method for obtaining transparent silica glass by a sol-gel method from a silica sol mixed solution composed of tetramethoxysilane or tetraethoxysilane and a silica sol solution containing silica fine particles.
  • Patent Document 3 in a method for producing transparent silica glass using silicon alkoxide and silica glass fine particles as main raw materials, heat treatment at 200 ° C. to less than 1300 ° C. is performed in an oxygen gas-containing atmosphere and further increased to 1700 ° C. or higher. It is shown that the heat treatment for heating is performed in an atmosphere containing hydrogen gas, and the reduced-pressure atmosphere heat treatment is performed between the two heat treatments.
  • these conventional sol-gel methods not only have problems in the dimensional accuracy and durability of the produced silica glass, but are not so inexpensive in terms of cost.
  • Patent Document 4 at least two different silica glass particles, for example, silica glass fine powder and silica glass particles are mixed to form a water-containing suspension, then pressure-molded, and sintered at high temperature to contain silica.
  • a method of obtaining a composite is shown.
  • opaque silica is produced by preparing a mixed liquid (slurry) containing silica glass particles having a size of 100 ⁇ m or less and silica glass granules having a size of 100 ⁇ m or more, injecting the mixture into a mold, and then drying and sintering.
  • a method of making a glass composite is shown.
  • these conventional slip casting methods have a large shrinkage of the molded body in the drying process and the sintering process, and it has not been possible to produce a thick silica glass molded body with high dimensional accuracy.
  • the method for producing a silica glass molded body from a powder raw material has the above-described problems. Therefore, even now, as a method for producing a silica crucible for producing single crystal silicon for LSI, production methods as described in Patent Document 6 and Patent Document 7 are used. In these methods, the ultra-pure natural quartz powder or synthetic cristobalite powder is put into a rotating carbon mold, and after molding, the carbon electrode is pushed in from the top, and the carbon electrode is energized. In this method, arc discharge is caused to raise the ambient temperature to the melting temperature range of quartz powder (estimated to be about 1800 to 2100 ° C.) to melt and sinter the quartz raw material powder.
  • Patent Document 8 discloses an outer layer made of natural quartz glass and an intermediate layer made of synthetic quartz glass having a high aluminum concentration by an arc discharge melting method of silica powder raw material (the atmosphere during melting is estimated to be air).
  • a silica crucible having an inner three-layer structure made of high-purity synthetic quartz glass is shown. And the effect of preventing impurity migration by the intermediate layer is shown.
  • this effect of preventing the migration of impurities is small, and when the outer layer contains high-concentration alkali metal elements Li, Na, K, etc., it is difficult to significantly suppress the diffusion of these elements. .
  • Patent Document 9 discloses a technique for reducing bubbles in the melted quartz crucible wall by sucking under reduced pressure from the outer periphery of the molding die during arc discharge melting of the silica powder raw material compact. Yes.
  • the dissolved gas in the melted quartz crucible wall could not be completely removed by simply vacuuming the air present in the silica powder.
  • only crucibles with a large residual gas of O 2 or H 2 O could be obtained.
  • Patent Document 10 discloses a silica crucible having a three-layer structure having an inner layer made of translucent quartz glass manufactured by an arc discharge melting method.
  • a silica crucible having a three-layer structure having an inner layer made of translucent quartz glass manufactured by an arc discharge melting method.
  • a silica container containing silica as a main component which has high dimensional accuracy and high durability, and suppresses the gas to be released, is relatively inexpensive. It is an object of the present invention to provide a method for producing a silica container, which can be produced at low cost, using low-grade silica powder as a main raw material, and to provide such a silica container.
  • a substrate having at least silica as a main component and having rotational symmetry, an intermediate layer formed on the inner wall surface of the substrate, and the intermediate A method of manufacturing a silica container comprising an inner layer formed on an inner wall surface of a layer, the step of preparing a first raw material powder that is silica particles for forming the substrate, and forming the intermediate layer A step of adding at least one of an Al compound and a compound powder serving as a crystal nucleating agent for crystallization of silica glass as an additive to the second raw material powder, which is a silica particle, and rotational symmetry.
  • the first raw material powder is introduced into the inner wall of the outer mold frame while rotating the outer mold frame formed with the decompression holes distributed on the inner wall, and the inner wall of the outer mold frame Temporary molding to a predetermined shape according to the And introducing the second raw material powder to which the additive is added into the inner wall of the base temporary molded body, and temporarily forming the intermediate powder into a predetermined shape according to the inner wall of the base temporary molded body.
  • the layer and the intermediate layer temporary molded body are depressurized from the outer peripheral side of the base temporary body by depressurizing by the step of forming the layer temporary molded body and the decompression hole formed in the outer mold.
  • the outer peripheral portion of the base body temporary body is made a sintered body, and the base body temporary
  • the inner part of the molded body and the intermediate layer temporary molded body are formed of a molten glass body, and the substrate and the intermediate layer are formed.
  • the inner layer is formed of crystalline silica from the inner side of the substrate. The silica purity is higher than that of the first raw material powder.
  • the gas (gas molecule) dissolved in the manufactured silica container can be suppressed. Therefore, when the silica container is used, gas molecules released from the silica container can be suppressed, so that adverse effects due to the gas molecules on the contents accommodated in the silica container can be reduced.
  • a silica container having a high dimensional accuracy and a high durability has the ability to sufficiently prevent impurities from being contaminated in the contained material while using a low-purity base material, with a small amount of energy consumption. It can be manufactured with high productivity and low cost.
  • the atmospheric gas in the step of forming the substrate and the intermediate layer from the preliminarily molded the substrate and the intermediate layer composed mainly of an inert gas, 1 vol H 2 gas. It is preferable to use a mixed gas containing at least%.
  • the atmospheric gas in the step of forming the substrate and the intermediate layer from the preliminarily molded substrate and the intermediate layer composed mainly of an inert gas, 1 vol H 2 gas. If the mixed gas contains at least%, it is possible to effectively reduce the dissolved amount of H 2 O molecules and O 2 molecules dissolved in the substrate among the gases dissolved in the manufactured silica container.
  • the atmospheric gas in the step of forming the inner layer is mainly composed of an inert gas and O 2 gas in an amount of 1 to 30 vol. % Containing mixed gas.
  • the atmosphere gas in the step of forming the inner layer is mainly composed of an inert gas and O 2 gas is 1 to 30 vol. If the mixed gas contains 1%, an inner layer with few carbon (C) fine particles can be obtained.
  • the atmospheric gas in the step of forming the inner layer is mainly composed of an inert gas and H 2 gas in an amount of 1 to 30 vol. % Containing mixed gas.
  • the atmosphere gas in the step of forming the inner layer is mainly composed of an inert gas and H 2 gas is 1 to 30 vol. If the mixed gas contains 1%, it is possible to effectively reduce the dissolved amount of H 2 O molecules and O 2 molecules dissolved in the inner layer, among the gases dissolved in the manufactured silica container.
  • the silica purity of the first raw material powder is 99.9 to 99.999 wt. %.
  • the silica purity of the first raw material powder as a raw material is 99.9 to 99.999 wt. %, It is possible to sufficiently prevent impurities from being contained in the contained items even if the purity is relatively low. Therefore, the raw material powder can be prepared at a very low cost.
  • the third raw material powder includes a step of containing at least one element of Ca, Sr, and Ba, and the total element concentration of Ca, Sr, and Ba to be contained is 50 to 5000 wt. It is preferable to set it as ppm.
  • the method further includes a step of forming a coating layer containing at least one element of Ca, Sr, and Ba on the inner surface side of the inner layer, and the total of Ca, Sr, and Ba contained in the coating layer.
  • the element concentration is preferably 5 to 500 ⁇ g / cm 2 .
  • the third raw material powder contains at least one element of Ca, Sr and Ba with a total element concentration of 50 to 5000 wt. at least in the case of containing as ppm, and forming a coating layer further containing at least one element of Ca, Sr, Ba on the inner surface side of the inner layer at a total element concentration of 5 to 500 ⁇ g / cm 2 If either one is performed, when the manufactured silica container is used at a high temperature such as 1300 to 1600 ° C., the inner layer is recrystallized to further reduce impurity contamination in the contained material. In addition, the etching and dissolution of the inner layer surface can be suppressed.
  • the said silica container shall be used as a crucible for silicon single crystal pulling.
  • the silica container manufactured by the method for manufacturing a silica container of the present invention can be suitably used as a crucible for pulling up a silicon single crystal.
  • the total input energy and the total cost for manufacturing the silicon single crystal can be reduced.
  • gas molecules dissolved in the manufactured silica container can be suppressed, gas molecules released from the silica container can be suppressed, and the adverse effect of the gas molecules on the silicon single crystal to be pulled up can be reduced. Can do.
  • the present invention has a rotational symmetry, a base made of silica having a white opaque layer part containing at least a gas bubble in the outer peripheral part, an intermediate layer formed on the inner wall surface of the base and made of silica, A silica container formed on an inner wall surface of an intermediate layer and comprising an inner layer made of transparent silica glass that is substantially colorless and transparent and does not contain bubbles, wherein the substrate has an element concentration of Li, Na, and K Of 300 wt.
  • the H 2 O molecules released when heated to 1000 ° C. under vacuum are 3 ⁇ 10 17 molecules / cm 3 or less, and the intermediate layer contains 10 to 1000 wt.
  • the inner layer contains OH groups in an amount of 1 to 200 wt.
  • the concentration of each element of Li, Na, and K is 60 wt. ppb or less, and each element concentration of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ta, and W is 30 wt.
  • a silica container characterized by being ppb or less.
  • Such a silica container is a low-cost silica container that has the ability to sufficiently prevent impurities from being contaminated, and has high dimensional accuracy and durability. It can be.
  • the release thereof is also suppressed, and the adverse effect of the H 2 O molecules on the contents stored in the silica container can be reduced. it can.
  • the substrate gases released when heated to 1000 ° C. under vacuum
  • the O 2 molecule is a 1 ⁇ 10 15 molecules / cm 2 or less
  • the H 2 O molecule 1 ⁇ 10 17 molecules / cm 3 or less and is 5 ⁇ 10 16 molecules / cm 3 or less for H 2 molecules
  • a 5 ⁇ 10 16 molecules / cm 3 or less for CO molecule the CO 2 molecules in 1 ⁇ 10 16 molecules / cm 3 or less
  • the amount of gas released when the substrate is heated to 1000 ° C. under vacuum is as described above, each gas molecule dissolved in the substrate is suppressed. The adverse effect of each gas molecule can be further reduced.
  • the intermediate layer has an OH group content of 30 to 300 wt. It is contained at a concentration of ppm, and Al is 30 to 300 wt. in a concentration of ppm, and the crystal nucleating agent is 30 to 300 wt. It is preferable to contain it at a concentration of ppm. Thus, if the intermediate layer contains OH groups, Al, and a crystal nucleating agent at the above concentrations at the same time, it is possible to further reduce the contamination of impurities in the contained material more effectively. .
  • the crystal nucleating agent is CaO, MgO, BeO, ZrO 2 , HfO 2, Al 2 O 3, ZrB 2, HfB 2, TiB 2, LaB 6, ZrC, HfC, TiC, TaC, ZrN, HfN, TiN, Any one or more of TaN is preferable.
  • the crystal nucleating agent is any one or more of the above compounds, it can more effectively impart an impurity diffusion preventing effect in the intermediate layer, and impurity contamination in the contained material Can be further reduced.
  • the inner layer gas release upon heating to 1000 ° C. under vacuum, and the 1 ⁇ 10 15 molecules / cm 2 or less for O 2 molecules, H 2 O molecules for 3 ⁇ 10 17 molecules / cm 3 or less, and is 5 ⁇ 10 16 molecules / cm 3 or less for H 2 molecules, and a 5 ⁇ 10 16 molecules / cm 3 or less for CO molecule, the CO 2 molecules in 1 ⁇ 10 16 molecules / cm 3 or less Preferably there is.
  • the amount of gas released when the inner layer is heated to 1000 ° C. under vacuum is as described above, each gas molecule dissolved in the inner layer is suppressed, so that the container accommodated in the silica container The adverse effect of each gas molecule on the object can be further reduced.
  • the inner layer contains at least one element of Ca, Sr, and Ba, and the total element concentration of the contained Ca, Sr, and Ba is 50 to 5000 wt. Preference is given to ppm.
  • the inner layer further has a coating layer containing at least one element of Ca, Sr, and Ba on the inner surface side, and the total element concentration of Ca, Sr, and Ba contained in the coating layer is It is preferably 5 to 500 ⁇ g / cm 2 .
  • the inner layer contains at least one element of Ca, Sr, and Ba, with a total element concentration of 50 to 5000 wt. at least a coating layer containing at least one element of Ca, Sr, Ba on the inner surface side of the inner layer at a total element concentration of 5 to 500 ⁇ g / cm 2. If either one is satisfied, when the silica container is used at a high temperature such as 1300 to 1600 ° C., the inner layer can be recrystallized to further reduce the contamination of impurities contained therein. At the same time, etching and dissolution of the inner layer surface can be suppressed.
  • dissolves in the manufactured silica container can be suppressed. Therefore, when the silica container is used, gas molecules released from the silica container can be suppressed, so that adverse effects due to the gas molecules on the contents accommodated in the silica container can be reduced.
  • a silica container with the ability to sufficiently prevent impurities from being contained and having high dimensional accuracy and durability is manufactured with low energy consumption, high productivity and low cost. can do.
  • silica container if it is a silica container according to the present invention, it is a low-cost silica container, but it has the ability to sufficiently prevent impurities from being contaminated, and has low dimensional accuracy and high durability. It can be a silica container.
  • gas molecules such as H 2 O molecules dissolved in the silica container are suppressed, the release thereof is also suppressed, and the adverse effect of the gas molecules on the contents stored in the silica container is reduced. be able to.
  • the conventional production of silica containers has a problem that a large amount of carbon dioxide is discharged due to a large input energy in the production such as high processing temperature and heat treatment temperature.
  • the cost is high because the ultra-high purity quartz raw material powder is used in the entire container.
  • the present inventors have studied in view of such problems, and have found the following problems.
  • the first problem is to make the amount of dissolved gas small (low emission gas). This is because, when a gas molecule such as O 2 gas, H 2 gas, H 2 O gas, CO gas, and CO 2 gas is taken into the silica container, in the case of a silica container used for pulling up a silicon single crystal, a silicon crystal At the time of fabrication, such gas molecules are released into the silicon melt and become bubbles and are taken into the grown silicon single crystal.
  • the first problem is to reduce the amount of gas molecules released from the silica container. Then, among the gas molecules, conventionally, in particular often dissolved amount of the H 2 O gas, and particularly central object to reduce the dissolved the H 2 O gas.
  • a silica container such as a crucible or boat for melting metal silicon and producing silicon crystals
  • the silica container has a multi-layer structure
  • the outer side of the container is a porous white opaque silica glass
  • the inner side of the container is a colorless transparent silica glass having substantially few bubbles.
  • silica containers such as crucibles and boats for producing silicon crystals have been required to have large silica containers as the diameter of silicon crystals has increased, and at a high temperature (for example, 1400 to 1600 ° C.) when melting metal silicon. It is a third problem to prevent the silica container itself from being softened and deformed at a degree).
  • the fourth problem is to provide the silica container with an impurity adsorption / fixing action and an impurity shielding (diffusion prevention) action so that the impurities contained in the silica container do not diffuse into the silicon melt.
  • the components of the silica container itself are dissolved in the silicon melt. Therefore, when oxygen element is taken into the silicon crystal, for example, in the case of manufacturing a solar silicon device, the photoelectric conversion efficiency is improved. There is a problem such as causing a decrease. Accordingly, it is a fifth problem that the inner surface of the silica container has a characteristic that it is difficult to be dissolved in the silicon melt (having etching resistance).
  • the above five technical problems have to be solved simultaneously at a lower cost than a silica container such as a high-purity single crystal silicon pulling crucible by a conventional manufacturing method.
  • the sixth object is to use a low-cost silica raw material that does not require a high-purity treatment and to provide a low-cost manufacturing method.
  • silica container solar grade crucible
  • metal silicon melting container used as a material for solar cells (solar power generation, solar power generation)
  • the present invention is not limited to this, and can be widely applied to all silica containers having rotational symmetry having silica as a main constituent.
  • FIG. 2 shows a schematic cross-sectional view of an example of a silica container according to the present invention.
  • the silica container 71 according to the present invention has rotational symmetry, and its basic structure is a three-layer structure including a base 51, an intermediate layer 56, and an inner layer 58 from the outer layer side.
  • the base 51 is a layer responsible for durability such as heat distortion resistance
  • the intermediate layer 56 is an impurity diffusion prevention layer
  • the inner layer 58 is a layer responsible for etching resistance to the contents. It is positioned as.
  • the silica container of this invention may further contain layers other than these, as long as it has at least these layers.
  • the base 51, the intermediate layer 56, and the inner layer 58 constituting the silica container 71 will be specifically described.
  • the base 51 has a portion (hereinafter, also referred to as an opaque layer portion) 51a made of a white opaque layer containing bubbles at least on the outer peripheral portion thereof.
  • a portion (hereinafter also referred to as a transparent layer portion) 51b made of a transparent or translucent layer may exist in a portion inside the white opaque layer portion 51a. This makes it possible to improve the heat uniformity inside the silica container 71 under heating.
  • the silica purity of the substrate 51 of the present invention is 99.9 to 99.999 wt. % And a relatively low purity. If the silica container of the present invention is used, the contamination of impurities contained in the container to be accommodated can be sufficiently prevented while the base 51 is made into a silica container having such a silica purity and a low cost.
  • the base 51 has a total element concentration of alkali metal elements Li, Na, and K of 300 wt. It shall be less than ppm.
  • the total element concentration of the alkali metal elements Li, Na, and K contained in the base 51 is 300 wt. Even relatively high ones such as ppm or less can sufficiently prevent impurity contamination in the accommodation.
  • the total element concentration of the alkali metal elements Li, Na, and K is 300 wt. If it is ppm or less, thermal deformation at high temperature can be suppressed. In this case, at the same time, aluminum (Al) element is added to the substrate 51 at 30 to 3000 wt.
  • the viscosity of the silica glass at high temperature can be improved, and the heat distortion resistance of the silica container 71 at high temperature can be further improved.
  • the silica container 71 is often used under high temperature and reduced pressure, and at this time, it is necessary to reduce the amount of gas released from the silica container 71.
  • the substrate 51 is assumed to have 3 ⁇ 10 17 molecules / cm 3 or less of H 2 O molecules released when heated to 1000 ° C. under vacuum. Furthermore, gas emission when heated at 1000 ° C.
  • O 2 molecule is a 1 ⁇ 10 15 molecules / cm 2 or less for, and a 1 ⁇ 10 17 molecules / cm 3 or less for H 2 O molecules
  • H 2 molecules is a 5 ⁇ 10 16 molecules / cm 3 below, and a 5 ⁇ 10 16 molecules / cm 3 or less for CO molecule, and more preferably about CO 2 molecule is 1 ⁇ 10 16 molecules / cm 3 or less .
  • the adverse effects of the gas molecules on the contents accommodated in the silica container can be reduced.
  • the silica container 71 of the present invention is used for pulling up a silicon single crystal, when the above gas release occurs, it is taken into the silicon crystal, and a structural defect such as a void or a pinhole is generated in the crystal.
  • this adverse effect can be reduced.
  • the intermediate layer 56 is formed on the inner wall surface of the base 51 and is made of silica.
  • a crystal nucleating agent crystal nucleating agent
  • heat-resistant ceramic particles high melting point compound powder having a melting point of about 2000 ° C.
  • oxides such as CaO, MgO, BeO, ZrO 2 , HfO 2 , Al 2 O 3 , boride as ZrB 2 , HfB 2 , TiB 2 , LaB 6 , carbide as ZrC, HfC, TiC, TaC, nitride as at least one of ZrN, HfN, TiN, TaN If it is heat-treated at about 1400-1600 ° C.
  • the concentration of the OH group, Al, and crystal nucleating agent contained in the intermediate layer 56 is 30 to 300 wt. ppm, Al is 30 to 300 wt. ppm, crystal nucleating agent is 30-300 wt. It is preferable to set it as ppm. Moreover, it is more preferable to satisfy these simultaneously.
  • the details of the mechanism by which Al, crystal nucleating agent, and OH group prevent migration and diffusion of impurity metal elements in silica glass are unknown, but by replacing Al with Si, the cation (cation) of the impurity metal element Is presumed to prevent adsorption and diffusion from the viewpoint of maintaining the charge balance of the silica glass network.
  • the crystal nucleating agent is a crystal nucleus of cristobalite, opal and other silica minerals when the silica container is used at a high temperature of 1400 to 1600 ° C., and these fine crystals are generated in the silica glass.
  • the diffusion coefficient of the impurity metal element is greatly reduced by making glass ceramics.
  • the OH group has an effect of adsorbing or preventing diffusion of these impurity metal elements by substitution of hydrogen ions and metal ions.
  • the intermediate layer 56 is white opaque or colorless and transparent silica glass for shielding (shielding) diffusion and movement of impurity metal elements contained in the substrate into the inner layer.
  • the intermediate layer 56 contains 10 to 1000 wt. Contains at a concentration of ppm.
  • the intermediate layer 56 contains at least one of Al and a compound serving as a crystal nucleating agent for crystallization of silica glass with a total content of 10 to 1000 wt. Contains in the ppm range.
  • the impurity metal element can be adsorbed and fixed.
  • the thickness of the intermediate layer 56 is not particularly limited, but is preferably 0.1 to 5 mm. If the thickness of the intermediate
  • the OH group concentration is adjusted by adjusting the OH group contained in the raw material powder (that is, the second raw material powder 12) for forming the intermediate layer 56, or by melting in the manufacture of the silica container described later.
  • -It can be performed by changing the atmosphere, temperature, and time conditions of the sintering process.
  • the upper limit of the OH group concentration contained in the intermediate layer 56 is set to 1000 wt. If it is made into ppm, it can also suppress that the fall of the viscosity of the silica glass under the high temperature by the increase in OH group density
  • the inner layer 58 is made of transparent silica glass that is formed on the inner wall surface of the intermediate layer 56 and is substantially colorless and transparent without containing bubbles.
  • the inner layer 58 contains 1 to 200 wt.
  • the concentration of each element of Li, Na, and K is 60 wt. ppb or less, and each element concentration of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ta, W is 30 wt. ppb or less.
  • the inner layer 58 has an OH group of 30 to 100 wt.
  • the concentration of each element of Li, Na, and K is 20 wt. ppb or less, and each element concentration of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ta, W is 10 wt. It is preferably ppb or less.
  • the inner layer 58 contains 30-100 wt. If it is contained at a concentration of ppm, the diffusion of the impurity metal element can be more effectively suppressed, and the adverse effect of the impurity metal element on the contents contained in the silica container can be reduced more effectively. Can do. Further, if the element concentrations of Li, Na, K, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ta, and W in the inner layer 58 are as described above, Moreover, the adverse effect of the impurity metal element on the contents accommodated in the silica container can be further reduced.
  • the inner layer 58 is gas released when heated to 1000 ° C. under vacuum, and the 1 ⁇ 10 15 molecules / cm 2 or less for O 2 molecules, H 2 O molecules for 3 ⁇ 10 17 molecules / cm 3 or less, and is 5 ⁇ 10 16 molecules / cm 3 or less for H 2 molecules, and a 5 ⁇ 10 16 molecules / cm 3 or less for CO molecule, the CO 2 molecules in 1 ⁇ 10 16 molecules / cm 3 or less Preferably there is. In this way, if each gas molecule dissolved in the inner layer 58 is suppressed, the adverse effect of each gas molecule on the contents accommodated in the silica container can be further reduced.
  • the silica container 71 when used as a crucible for pulling up a silicon single crystal by reducing the H 2 O gas (H 2 O molecule) and the O 2 gas (O 2 molecule) contained in the inner layer 58, Release of moisture and oxygen at the time of melting silicon can be reduced, so that the oxygen concentration in the silicon crystal can be reduced and the generation of crystal defects such as voids and pinholes can be reduced.
  • the concentration of H 2 O molecules and O 2 molecules contained in the inner layer 58 cuts out the measurement sample from the inner layer 58, and the gas release amount of the measurement sample is heated to 1000 ° C. under vacuum.
  • the H 2 O gas is preferably 3 ⁇ 10 17 molecules / cm 3 or less and the O 2 gas is preferably 1 ⁇ 10 15 molecules / cm 2 or less.
  • the silica container 71 of the present invention is used as a crucible for pulling a silicon single crystal that requires high durability, such as a container for continuously pulling a silicon single crystal (multi-pulling) in the production of photovoltaic devices.
  • group 2A group 2 elements calcium (Ca), strontium (Sr), and barium (Ba) is added to the inner layer 58. It is preferable to contain.
  • the total element concentration of Ca, Sr, and Ba contained in the inner layer 58 is 50 to 5000 wt. Preference is given to ppm.
  • the group 2 element to be contained is more preferably Sr or Ba, and particularly preferably Ba from the point that it is difficult to incorporate into the silicon single crystal.
  • the inner layer 58 contains at least one of Ca, Sr, and Ba
  • the inner surface of the inner layer 58 that is, the inner surface of the silica container is recrystallized at a temperature of about 1500 ° C. when silicon is melted.
  • a cristobalite it is possible to improve the silicon melt etching resistance.
  • the same effect can be obtained by having a coating layer containing at least one element of Ca, Sr, and Ba inside the inner layer 58.
  • the total element concentration of Ca, Sr, and Ba contained in the coating layer is preferably 5 to 500 ⁇ g / cm 2 .
  • Such crystallization accelerators are disclosed in documents (Japanese Patent No. 3100836 and Japanese Patent No. 3046545).
  • silica container of this invention which can manufacture the above silica containers is demonstrated more concretely.
  • a method for producing a silica container (solar grade crucible) that can be manufactured at low cost and can be used as a container for melting and single crystal pulling of metal silicon (Si), which is used as a material for photovoltaic power generation devices, etc. explain.
  • the outline of the manufacturing method of the silica container 71 which concerns on this invention is shown in FIG.
  • the 1st raw material powder 11 which is a silica particle is prepared (process 1).
  • the first raw material powder 11 is a main constituent material of the base 51 in the silica container (see FIG. 2) according to the present invention.
  • the first raw material powder can be produced, for example, by pulverizing and sizing the silica lump as follows, but is not limited thereto.
  • a natural silica lump (naturally produced crystal, quartz, silica, siliceous rock, opal stone, etc.) with a diameter of about 5 to 50 mm is heated in a temperature range of 600 to 1000 ° C. for about 1 to 10 hours in an air atmosphere.
  • the natural silica mass is put into water, taken out after rapid cooling, and dried. This process facilitates the subsequent crushing and sizing process by a crusher or the like, but the process may proceed to the pulverization process without performing the heating and quenching process.
  • the natural silica mass is pulverized and sized by a crusher or the like, and the particle size is preferably adjusted to 10 to 1000 ⁇ m, more preferably 50 to 500 ⁇ m to obtain natural silica powder.
  • this natural silica powder is put into a rotary kiln composed of a silica glass tube having an inclination angle, and the inside of the kiln is made into an atmosphere containing hydrogen chloride (HCl) or chlorine (Cl 2 ) gas, and is kept at 700 to 1100 ° C.
  • the high-purity treatment is performed by heating for about 1 to 100 hours. However, in a product application that does not require high purity, the process may proceed to the next process without performing the purification process.
  • the first raw material powder 11 obtained after the above steps is crystalline silica.
  • amorphous silica glass scrap may be used as the first raw material powder 11. it can.
  • the particle diameter of the first raw material powder 11 is preferably 10 to 1000 ⁇ m, and more preferably 50 to 500 ⁇ m.
  • the silica purity of the first raw material powder 11 is 99.9 wt. % Or more, preferably 99.99 wt. % Or more is more preferable.
  • the silica purity of the 1st raw material powder 11 shall be 99.999 wt. Even if it is a thing with comparatively low purity as% or less, the manufactured silica container can fully prevent the impurity contamination to the accommodation to accommodate. Therefore, a silica container can be manufactured at a lower cost than before.
  • the concentration of OH groups contained in the first raw material powder 11 is 10 to 1000 wt. It is preferable to set it to about ppm.
  • the OH group contained in the first raw material powder 11 can be adjusted depending on the gas atmosphere, treatment temperature, and time in the subsequent drying process, which is included in the natural quartz from the beginning, or moisture mixed in the intermediate process. .
  • Silica glass synthesized by the flame hydrolysis method or manufactured by the flame Bernoulli method has 200 to 2000 wt. ppm OH groups are contained, and the OH group concentration can be adjusted by mixing an appropriate amount of these OH group-containing amorphous silica powders.
  • either the Al compound or the compound powder serving as a crystal nucleating agent may be added to the first raw material powder 11.
  • the second raw material powder 12 that is silica particles for forming the intermediate layer 56 and the additive 21 for crystallization of an Al compound and silica glass.
  • At least one of compound powders to be a crystal nucleating agent is prepared (Step 2).
  • additive namely, compound powder used as a crystal nucleating agent for crystallization of Al compound and silica glass
  • mixed powder 31 step 3
  • the second raw material powder 12 which is silica particles for forming the intermediate layer 56 is preferably higher in purity than the first raw material powder 11, but is not limited thereto.
  • the preparation of the second raw material powder 12 can be performed, for example, in substantially the same manner as the first raw material powder 11. That is, it can be performed as follows.
  • a natural silica lump (naturally produced crystal, quartz, silica, siliceous rock, opal stone, etc.) with a diameter of about 5 to 50 mm is heated in a temperature range of 600 to 1000 ° C. for about 1 to 10 hours in an air atmosphere.
  • the natural silica mass is put into water, taken out after rapid cooling, and dried. This process facilitates the subsequent crushing and sizing process by a crusher or the like, but the process may proceed to the pulverization process without performing the heating and quenching process.
  • the natural silica mass is pulverized and sized by a crusher or the like, and the particle size is preferably adjusted to 10 to 1000 ⁇ m, more preferably 50 to 500 ⁇ m to obtain natural silica powder.
  • this natural silica powder is put into a rotary kiln composed of a silica glass tube having an inclination angle, and the inside of the kiln is made into an atmosphere containing hydrogen chloride (HCl) or chlorine (Cl 2 ) gas, and is kept at 700 to 1100 ° C.
  • the high-purity treatment is performed by heating for about 1 to 100 hours.
  • the second raw material powder 12 obtained after the above steps is crystalline silica.
  • amorphous silica glass scrap may be used as the second raw material powder 12. it can.
  • the particle diameter of the second raw material powder 12 is preferably 10 to 1000 ⁇ m, and more preferably 50 to 500 ⁇ m.
  • the silica purity of the second raw material powder 12 is 99.999 wt. % Or more is preferable.
  • an intermediate A predetermined amount of an Al compound or a crystal nucleating agent is contained in the second raw material powder 12 for forming the layer 56.
  • the addition of Al can be obtained, for example, by using Al nitrate, acetate, carbonate, chloride or the like as a water or alcohol solution, putting silica powder in the solution, immersing it, and then drying.
  • Crystal nucleating agent can be used fine compound powder having a melting point of at least 2000 ° C., for example in the oxide CaO, MgO, BeO, ZrO 2 , HfO 2, Al 2 O 3, ZrB 2 in the boride, HfB 2, TiB 2,
  • carbides, ZrC, HfC, TiC, TaC, and nitrides may be ZrN, HfN, TiN, TaN, and the like.
  • a fine powder having a particle size of about 0.1 to 10 ⁇ m which is suitable for the use of a silica container, is mixed with a predetermined amount of silica powder.
  • the concentration of OH groups contained in the second raw material powder 12 is 10 to 1000 wt. It is preferable to set it to about ppm.
  • the OH group contained in the second raw material powder 12 can be adjusted depending on the gas atmosphere, treatment temperature, and time in the subsequent drying step, which is included in the natural quartz from the beginning, or moisture mixed in the intermediate step. .
  • Silica glass synthesized by the flame hydrolysis method or manufactured by the flame Bernoulli method has 200 to 2000 wt. ppm OH groups are contained, and the OH group concentration can be adjusted by mixing an appropriate amount of these OH group-containing amorphous silica powders.
  • the first raw material powder 11 is introduced into an outer mold frame having rotational symmetry for molding (step 4).
  • FIG. 3 sectional drawing showing the outline of the external frame which temporarily molds the 1st raw material powder 11 was shown.
  • the outer mold 101 is made of a heat-resistant ceramic such as graphite, alumina, silicon nitride, silicon carbide, and has rotational symmetry.
  • a decompression hole 103 is distributed and formed in the inner wall 102 of the outer mold 101.
  • the decompression hole 103 is continuous with the decompression passage 104.
  • a pressure reducing passage 105 also passes through a rotating shaft 106 for rotating the outer mold 101, and vacuuming can be performed therefrom.
  • the first raw material powder 11 is introduced into the inner wall 102 of the outer mold frame 101, the first raw material powder 11 is temporarily formed into a predetermined shape corresponding to the inner wall 102 of the outer mold frame 101, and a temporary molded body 41 of the base body. (See FIG. 4). Specifically, while rotating the outer mold 101, the first raw material powder 11 is gradually put into the inner wall 102 of the outer mold 101 from a raw material powder hopper (not shown), and the container is made using centrifugal force. Mold into shape. Moreover, the thickness of the temporary molded body 41 of the base body may be adjusted to a predetermined amount by bringing a plate-shaped inner mold (not shown) from the inside into contact with the rotating powder.
  • the method for supplying the first raw material powder 11 to the outer mold 101 is not particularly limited.
  • a hopper equipped with a stirring screw and a measuring feeder can be used.
  • the 1st raw material powder 11 with which the hopper was filled is stirred with the screw for stirring, and it supplies, adjusting a supply amount with a measurement feeder.
  • the second raw material powder 12 to which the additive 21 is added (that is, the mixed powder 31) is introduced into the inner wall of the temporary molding body 41 of the base, Temporarily forming into a predetermined shape corresponding to the inner wall of the temporary formed body 41 to form a temporary formed body 46 of the intermediate layer (see FIG. 5) (step 5).
  • the specific method for forming the intermediate layer temporary molded body 46 can be performed in substantially the same manner as in the case of forming the base temporary molded body 41 described above.
  • the mixed powder 31 is gradually put into the inner wall of the base temporary molded body 41 from a raw material powder hopper (not shown), Using a centrifugal force, the substrate is molded into a predetermined shape according to the inner wall of the temporary molded body 41 of the substrate. Further, the thickness of the temporary molded body 46 of the intermediate layer may be adjusted to a predetermined amount by bringing a plate-like inner mold (not shown) into contact with the rotating powder from the inside.
  • the supply method of this mixed powder 31 can also use the hopper provided with the screw for stirring and a measurement feeder similarly to the supply method of said 1st raw material powder 11, for example.
  • the base 51 and the intermediate layer 56 are formed by reduced pressure and discharge heating (step 6).
  • the base and intermediate layer temporary molded bodies 41 and 46 (base temporary molded bodies are formed by reducing the pressure through the decompression hole 103 formed in the outer mold 101. 41 and the intermediate layer temporary molded body 46) are degassed by depressurization from the outer peripheral side of the substrate temporary molded body 41, and heated from the inside of the substrate and intermediate layer temporary molded body by the discharge heating melting method.
  • the outer peripheral portion of the base temporary molded body 41 is a sintered body
  • the inner portion of the base temporary molded body 41 and the intermediate layer temporary molded body 46 are molten glass bodies.
  • the apparatus for forming the base body 51 and the intermediate layer 56 includes a rotary motor (not shown) and carbon that serves as a heat source for discharge melting (arc melting) in addition to the rotatable outer mold 101 having rotational axis symmetry. It consists of an electrode 212, an electric wire 212a, a high voltage power supply unit 211, and a lid 213. In addition, this apparatus can be used continuously when forming the inner layer 58 on the inner surface of the intermediate
  • the melting and sintering procedures of the base body and intermediate layer temporary molded bodies 41 and 46 are as follows. First, the outer mold frame 101 containing the base body and intermediate layer temporary molded bodies 41 and 46 is rotated at a constant speed while being removed. A gas vacuum pump (not shown) is activated to reduce the pressure from the outside of the temporary molded body 41 through the pressure reducing hole 103 and the pressure reducing passages 104 and 105 and to start applying electric power to the carbon electrode 212.
  • the inner surface portions of the base body and intermediate layer temporary formed bodies 41 and 46 (that is, the inner surface portion of the intermediate layer temporary formed body 46) It becomes the melting temperature range of silica powder (estimated to be about 1800-2000 ° C), and melting starts from the outermost layer.
  • the degree of vacuuming by the degassing vacuum pump increases (the pressure suddenly decreases), and the first raw material powder 11 and the mixed powder 31 (the second raw material to which the additive 21 is added) While the dissolved gas contained in the powder 12) is degassed, the change to the fused silica glass layer proceeds from the inside to the outside.
  • the entire region of the intermediate layer is melted to become a transparent or translucent layer, and the inner half of the total thickness of the substrate is melted to become a portion (transparent layer portion) 51b made of a transparent or translucent layer.
  • heating by applying electricity and depressurization by a vacuum pump are continued until the remaining outer half is sintered white opaque silica (opaque layer portion) 51a.
  • the degree of vacuum is preferably 10 3 Pa or less.
  • the atmosphere gas at the time of arc melting in the base 51 in which the intermediate layer 56 is formed is an inert gas such as nitrogen (N 2 ), argon (Ar), helium (He), etc. for the purpose of reducing the consumption of the carbon electrode 212.
  • the main component 1 vol hydrogen gas (H 2).
  • H 2 1 vol hydrogen gas
  • % Or more is preferably mixed, and 1 to 50 vol. % Mixing is more preferable. This is because, for example, oxygen gas (O 2 ), which is difficult to degas, reacts with hydrogen to produce water (H 2 O), and the water molecules have a larger diffusion coefficient than oxygen molecules. 56 is considered to be easily released to the outside.
  • hydrogen gas (H 2 ) since hydrogen gas (H 2 ) has a small molecular radius and a large diffusion coefficient, even if it is contained in the atmospheric gas, it is easily released to the outside of the substrate 51 and the intermediate layer 56. Further, when H 2 is contained in the atmosphere, there is an effect of reducing H 2 O gas, which is likely to be contained in a particularly large amount, among the dissolved gas from the inside of the base 51 and the intermediate layer 56.
  • the third raw material powder made of crystalline silica and having a silica purity higher than that of the first raw material powder 11 from the inside of the substrate 51 on which the intermediate layer 56 is formed.
  • the inner layer 58 is formed on the inner surface of the intermediate layer 56 by heating from the inside by a discharge heating melting method (step 7).
  • the basic formation method of the inner layer 58 follows the contents shown in Patent Document 6 and Patent Document 7, for example.
  • the apparatus for forming the inner layer 58 on the inner surface of the intermediate layer 56 is a rotatable outer mold 101 on which a base 51 on which the intermediate layer 56 having rotational axis symmetry is formed is installed.
  • a rotary motor (not shown) and a raw material powder hopper 303 containing the third raw material powder 13 for forming the inner layer 58, a stirring screw 304, a measuring feeder 305, and a heat source for discharge melting (arc melting) It consists of a carbon electrode 212, an electric wire 212a, a high voltage power supply unit 211, and a lid 213.
  • the outer mold 101 is set to a predetermined rotation speed, and a high voltage is gradually applied from the high-voltage power supply unit 211.
  • the inner layer 58 is gradually formed from the raw material hopper 303.
  • the third raw material powder (high-purity silica powder) 13 is sprayed from the upper part of the substrate 51 on which the intermediate layer 56 is formed.
  • discharge has started between the carbon electrodes 212, and the inside of the substrate 51 on which the intermediate layer 56 is formed is in the melting temperature range of silica powder (estimated to be about 1800 to 2000 ° C.).
  • the raw material powder 13 becomes silica fused particles and adheres to the inner surface of the intermediate layer 56.
  • the carbon electrode 212, the raw material powder inlet, and the lid 213 installed in the upper opening of the base 51 on which the intermediate layer 56 is formed have a mechanism in which the position can be changed to some extent with respect to the base 51 on which the intermediate layer 56 is formed. By changing these positions, the inner layer 58 can be formed on the entire inner surface of the intermediate layer 56 with a uniform thickness.
  • the atmosphere gas inside the base 51 on which the intermediate layer 56 during arc discharge melting for forming the silica glass transparent layer is formed is reduced in nitrogen gas (N 2 ), argon gas (Ar),
  • the main component is an inert gas such as helium gas (He), but hydrogen gas (H 2 ) 1-30 vol. %,
  • the inner layer 58 with fewer bubbles can be obtained.
  • the mixed gas has an H 2 content of 1 vol. % Or more, the effect of reducing bubbles contained in the inner layer 58 (transparent silica glass) can be further increased, and the H 2 content is 30 vol.
  • the bubble reduction effect of the inner layer 58 can be sufficiently obtained, and the cost of the mixed gas can be suppressed. At this time, dissolved H 2 O molecules can be effectively reduced by using a dry gas atmosphere containing no water vapor.
  • the carbon (C) carbon fine particles generated during arc discharge melting are oxidized to form CO and CO 2 , whereby the inner layer 58 with few carbon (C) fine particles can be obtained.
  • the mixed gas has an O 2 content of 1 vol. % Or more, the effect of reducing the carbon fine particles contained in the inner layer 58 (transparent silica glass) can be further increased, and the O 2 content is 30 vol. If it is less than or equal to%, the effect of reducing the carbon fine particles of the inner layer 58 can be sufficiently obtained, and consumption of the carbon electrode can be suppressed, which is also preferable from an industrial viewpoint. At this time, CO and CO 2 are generated as described above, but they can be removed for decompression.
  • silica powder after high-purification treatment or silica powder containing a specific element at a predetermined concentration is used as the third raw material powder 13, depending on the use of the finally produced silica container. It is possible. For example, if alkaline earth metal elements calcium (Ca), strontium (Sr), and barium (Ba) are contained in the raw material powder as an etchant, these elements are contained in the inner layer 58.
  • the inner layer 58 is recrystallized to form a cristobalite layer, preventing diffusion contamination of the impurity metal element contained in the substrate 51 to the object to be processed in the container, It becomes possible to reduce the etching and dissolution of the silica glass on the surface of the layer 58.
  • the silica container 71 of the present invention can be obtained, but the silica container is washed as follows as necessary.
  • silica container cleaning and drying For example, surface etching is performed with about 1 to 10% hydrofluoric acid aqueous solution (HF) for 5 to 30 minutes, then washed with pure water and dried in clean air to obtain a silica container.
  • HF hydrofluoric acid aqueous solution
  • a step of applying a solution containing at least one of calcium (Ca), strontium (Sr), and barium (Ba) to the inner surface of the inner layer 58 can be provided.
  • At least one or more of Ca, Sr, and Ba as a crystallization accelerator is applied (coated) to the inner surface of the inner surface portion (that is, the inner layer 58) of the manufactured silica container 71.
  • An aqueous solution or alcohol solution of any of these nitrates, chlorides, and carbonates of Ca, Sr, and Ba is prepared, and this is applied to the inner surface of the inner layer 58 and dried.
  • the total element concentration of Ca, Sr, and Ba is preferably 5 to 500 ⁇ g / cm 2 . This treatment may not be performed depending on the use of the silica container.
  • the silica container 71 according to the present invention shown in FIG. 2 as described above can be manufactured.
  • Example 1 According to the method for producing a silica container of the present invention shown in FIG. 1, a silica container was produced as follows.
  • the first raw material powder 11 was prepared as follows (step 1). 100 kg of natural silica was prepared, heated in an air atmosphere at 1000 ° C. for 10 hours, put into a water tank containing pure water, and rapidly cooled. This was dried and then pulverized using a crusher to obtain a particle size of 30 to 300 ⁇ m and a silica (SiO 2 ) purity of 99.999 wt. %, And a total weight of about 90 kg of silica powder (natural quartz powder).
  • the 2nd raw material powder 12 was prepared as follows (a part of process 2). About 3 kg of natural silica was prepared, heated in an air atmosphere at 1000 ° C. for 10 hours, charged into a water tank containing pure water, and rapidly cooled. This was dried and pulverized using a crusher. Further, it is purified by heat treatment in a hydrogen chloride-containing gas atmosphere, and has a particle size of 30 to 300 ⁇ m and silica (SiO 2 ) purity of 99.9999 wt. % And a total weight of about 2 kg of silica powder (natural quartz powder).
  • an aluminum nitrate aqueous solution was prepared as an additive 21 to be added to the second raw material powder 12 (part of step 2). This was mixed with the second raw material powder 12 and dried to obtain a mixed powder 31 (step 3).
  • the Al concentration in the second raw material powder 12 is 50 wt. It was set to be ppm.
  • the first raw material powder 11 is put into the inner wall 102 of the rotating cylindrical carbon outer mold frame 101 in which the decompression hole 103 is formed in the inner wall 102, and the outer
  • the shape of the first raw material powder 11 was adjusted so as to have a uniform thickness in accordance with the shape of the mold 101 to obtain a temporary molded body 41 of the base (step 4).
  • the mixed powder 31 (second raw material powder 12 to which the additive 21 has been added) is introduced into the inner wall of the base temporary molded body 41.
  • the mixed powder 31 was temporarily formed so as to have a uniform thickness in accordance with the shape of the inner wall to obtain a temporary formed body 46 of the intermediate layer (step 5).
  • the base 51 and the intermediate layer 56 were formed by discharge melting (arc melting) while reducing the pressure (step 6).
  • the base and intermediate layer temporary molded bodies 41 and 46 are depressurized from the outer peripheral side of the base temporary molded body 41 by reducing the pressure through the decompression hole 103 formed in the outer mold 101.
  • the outer peripheral portion of the base temporary molded body 41 is formed into a sintered body by heating at a high temperature from the inside of the base and intermediate layer temporary molded bodies 41 and 46 by a discharge heating melting method.
  • the inner portion of the temporary molded body 41 and the intermediate layer temporary molded body 46 were made of molten glass, and the base 51 and the intermediate layer 56 were formed.
  • the atmosphere gas was a dry nitrogen gas of 100 vol. %.
  • the inner layer 58 was formed by electric discharge melting (arc melting) (step 7).
  • the carbon electrode 212 was inserted into the base 51 on which the intermediate layer 56 formed in the outer mold 101 was formed, and the inner layer forming raw material supply port and the lid 213 were set. Thereafter, while the outer mold 101 is rotated, a synthetic cristobalite powder (particle size 100 to 300 ⁇ m, silica purity 99.99999%) is gradually added as the third raw material powder 13 while being discharged and heated by the carbon electrode 212 (electric arc) Heated). Atmosphere gas is 5 vol. % Nitrogen (nitrogen 95 vol.%).
  • the silica container 71 manufactured in this way is 3 wt. After washing with an aqueous hydrofluoric acid solution (HF) for 3 minutes, it was washed with pure water and dried.
  • HF aqueous hydrofluoric acid solution
  • Example 2 Although the silica container 71 was manufactured basically in the same manner as in Example 1, the following points were changed. First, Al was also added to the first raw material powder 11 as an additive. The Al concentration in the first raw material powder 11 is 50 wt. It adjusted so that it might become ppm. In the step of forming the base body 51 and the intermediate layer 56 from the temporary molded bodies 41 and 46 of the base body and the intermediate layer (step 6), the atmospheric gas is changed to 10 vol. % Nitrogen (nitrogen 90 vol.%).
  • Example 3 Although the silica container 71 was manufactured basically in the same manner as in Example 2, the following points were changed.
  • the second raw material powder 12 a synthetic silica glass powder (particle size: 30 to 300 ⁇ m) prepared by a flame hydrolysis method is used, and the content of OH groups contained in the intermediate layer 56 is set as in Example 1. Higher than 2, 200 wt. It adjusted so that it might become ppm. Further, the Al concentration as the additive 21 added to the second raw material powder 12 is increased, and 100 wt. It adjusted so that it might become ppm. Further, in the step of forming the base 51 and the intermediate layer 56 from the temporary molded bodies 41 and 46 of the base and the intermediate layer (step 6), the atmosphere gas is changed to hydrogen 5 vol. % Nitrogen (nitrogen 95 vol.%).
  • Example 4 Although the silica container 71 was manufactured basically in the same manner as in Example 3, the following points were changed.
  • the first raw material powder 11 was a low-cost low-purity silica powder (a silica (SiO 2 ) purity 99.99% grade product).
  • the content of OH groups contained in the synthetic silica glass of the second raw material powder 12 is further increased than that in Example 3, and the content of OH groups contained in the intermediate layer 56 is 400 wt. It adjusted so that it might become ppm.
  • the Al concentration as the additive 21 added to the second raw material powder 12 is further increased from that in Example 3, and 400 wt. It adjusted so that it might become ppm.
  • the third raw material powder 13 was natural quartz powder (particle size 100 to 300 ⁇ m, silica purity 99.9999%).
  • Example 5 Basically, the silica container 71 was manufactured in the same manner as in Example 1, but the following changes were made.
  • the low-cost low-purity silica powder (silica (SiO 2 ) purity 99.99% grade product, particle size 30 to 300 ⁇ m) was used as the first raw material powder 11.
  • the content of OH groups contained in the intermediate layer 56 is 50 wt. It adjusted so that it might become ppm.
  • an additive 21 to be added to the second raw material powder 12 200 wt.
  • the atmospheric gas is changed to 10 vol. % Nitrogen (nitrogen 90 vol.%).
  • the third raw material powder 13 was natural quartz powder (particle size 100 to 300 ⁇ m, silica purity 99.9999%). Further, the barium chloride solution was applied to the inner surface of the inner layer 58 so that the final concentration of Ba was 100 ⁇ g / cm 2 .
  • the silica container 71 was manufactured basically in the same manner as in Example 5, the following changes were made.
  • the first raw material powder 11 was a low-cost low-purity silica powder (silica (SiO 2 ) purity 99.99% grade product, particle size 50 to 500 ⁇ m). Further, the first raw material powder 11 contains 50 wt. It added so that it might become a density
  • Example 7 Although the silica container 71 was manufactured basically in the same manner as in Example 5, the following changes were made. In the step of forming the inner layer 58 by discharge melting (arc melting) (step 7), the atmospheric gas is changed to 10 vol. % Nitrogen (nitrogen 90 vol.%). Instead of applying the barium chloride solution to the inner surface of the inner layer 58, the final Ba concentration of the inner layer 58 is 300 wt. Barium nitrate was added to the third raw material powder 13 so as to have ppm.
  • Example 8 As in Example 7, except that in the step of forming the inner layer 58 (Step 7), the atmospheric gas was changed to hydrogen 30 vol.
  • the silica container 71 was manufactured as nitrogen containing nitrogen (nitrogen 70 vol.%).
  • a silica container (silica crucible) was prepared according to a conventional method. That is, the portion corresponding to the substrate of the silica container of the present invention was also formed by discharge melting (arc melting) using high-purity raw material powder. Moreover, a layer corresponding to the intermediate layer of the silica container of the present invention was not formed.
  • a raw material powder corresponding to the first raw material powder silica purity of 99.9999 wt. % Natural quartz powder (particle size: 30 to 300 ⁇ m) having a purity of at least%.
  • high purity natural quartz powder is introduced directly into the rotating frame made of carbon, and the quartz powder layer is utilized by utilizing centrifugal force in the rotating frame. This was discharged and melted with a carbon electrode to form an outer layer portion (corresponding to the substrate 51 of the present invention). This is 60 minutes, and the temperature of the outer layer is estimated to be about 2000 ° C.
  • a silica purity of 99.99999 wt. % Of high-purity synthetic cristobalite powder (particle size 50 to 300 ⁇ m) is prepared, and this high-purity synthetic cristobalite powder is sprayed from the hopper on the inner surface of the outer layer, especially in an air atmosphere where humidity is not adjusted.
  • An inner layer portion (corresponding to the inner layer 58 in the silica container 71 of the present invention) was formed by electrode discharge melting.
  • the outer layer part (corresponding to the substrate 51 of the present invention) is formed of low-purity silica, and the inner layer part (corresponding to the inner layer 58 in the silica container 71 of the present invention) is formed.
  • a silica container was manufactured by forming with high purity silica. That is, as in Comparative Example 1, however, low purity natural quartz powder having a silica purity of 99.99% was used as the silica powder for the outer layer portion. Further, as the silica powder for the inner layer portion, highly purified natural quartz powder (particle size 100 to 300 ⁇ m, silica purity 99.9999 wt.%) was used.
  • ICP-AES plasma emission analysis
  • ICP-MS Inductively Coupled Plasma-Plassed Coupled Plasma-Plasma
  • AAS atomic absorption spectrophotometry
  • the thickness of the substrate and inner layer was determined by measuring the container cross section at half the full height of the side wall of the silica container on a scale.
  • H 2 , H 2 O, CO, and CO 2 were considered to have been released in total, and thus per unit volume. Expressed as the number of released molecules (molecules / cm 3 ).
  • the details of the measurement method follow the following literature. Nasu, S .; et al. (1990) “Gas release of various kinds of vitreous silica”, Journal of Illuminating Engineering of Japan, vol. 74, no. 9, pp. 595-600.
  • the H 2 gas as dissolved gas concentration in the silica glass, it was confirmed that the same value can be obtained by the following measuring method literature.
  • the manufactured silica container was washed and dried, and then placed in an electric furnace using a high-purity alumina board as a heat-resistant material and molybdenum disilicide as a heater, and subjected to heat treatment at 1450 ° C. for 12 hours. Subsequently, 100 ⁇ m of the inner surface portion of the container was washed away with a hydrofluoric acid (HF) aqueous solution.
  • HF hydrofluoric acid
  • Tables 1 to 5 and Tables 6 to 7 The production conditions, measured physical property values, and evaluation results of the silica containers produced in Examples 1 to 8 and Comparative Examples 1 and 2 are summarized in Tables 1 to 5 and Tables 6 to 7 below.
  • Table 6 shows analysis data on the amount of gas released from the substrate 51 and analysis data on the amount of gas released from the inner layer 58
  • Table 7 shows impurity analysis values on the inner layer 58.
  • Example 2 in the step of forming the base body 51 and the intermediate layer 56 from the temporary molded bodies 41 and 46 of the base body and the intermediate layer (Step 6), the atmospheric gas was changed to 10 vol. As a result, the amount of released H 2 O gas in the substrate could be reduced as compared with Example 1. Further, in Example 3, the impurity diffusion preventing effect could be improved as compared with Examples 1 and 2 by increasing the concentration of OH groups and Al in the intermediate layer 56.
  • the first raw material powder 11 for the substrate 51 is low-cost low-purity silica powder (silica purity 99.99%), but the OH group and Al concentration of the intermediate layer 56 are increased. As a result, the effect of preventing impurities could be sufficiently enhanced. As a result, the total amount of raw material costs was low, and it was possible to produce a silica container with sufficient performance at a low cost.
  • Example 5 as in Example 4, the first raw material powder 11 for the substrate 51 was low-cost, low-purity silica powder (silica purity 99.99%). The effect of preventing impurities could be further enhanced by the combined effect of the Al concentration and the crystal nucleating agent. In addition, by applying the Ba solution on the inner surface of the inner layer 58, the recrystallization rate of the inner surface was increased and the etching resistance could be improved.
  • Example 6 the etching resistance could be improved by further increasing the concentration of Ba applied to the inner surface of the inner layer 58 as compared with Example 5.
  • the outer layer portion (corresponding to the substrate 51 of the present invention) is formed of lower purity silica than Comparative Example 1 for the purpose of reducing the production cost of the silica container.
  • the amount of impurity diffusion to the inner surface of the container was large and the amount of gas released was also large.
  • the present invention is not limited to the above embodiment.
  • the above embodiment is merely an example, and the present invention has the same configuration as that of the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Glass Melting And Manufacturing (AREA)
  • Glass Compositions (AREA)
PCT/JP2010/002049 2009-05-26 2010-03-24 シリカ容器及びその製造方法 WO2010137221A1 (ja)

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JP2010540751A JP4903288B2 (ja) 2009-05-26 2010-03-24 シリカ容器及びその製造方法
CN201080016990.8A CN102395535B (zh) 2009-05-26 2010-03-24 二氧化硅容器及其制造方法
EP10780183.9A EP2436658A4 (en) 2009-05-26 2010-03-24 SILICONE CONTAINER AND MANUFACTURING METHOD THEREFOR
US13/055,865 US8420192B2 (en) 2009-05-26 2010-03-24 Silica container and method for producing the same
KR1020117026489A KR101315684B1 (ko) 2009-05-26 2010-03-24 실리카 용기 및 그 제조방법
US13/793,948 US8915096B2 (en) 2009-05-26 2013-03-11 Silica container and method for producing the same

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WO2013105165A1 (ja) * 2012-01-13 2013-07-18 信越石英株式会社 単結晶シリコン引き上げ用シリカ容器及びその製造方法
WO2013171937A1 (ja) * 2012-05-15 2013-11-21 信越石英株式会社 単結晶シリコン引き上げ用シリカ容器及びその製造方法
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JP2011121811A (ja) * 2009-12-10 2011-06-23 Shinetsu Quartz Prod Co Ltd シリカ容器及びその製造方法
JP2012136399A (ja) * 2010-12-27 2012-07-19 Covalent Materials Corp シリコン単結晶引上げ用シリカガラスルツボ
WO2013105165A1 (ja) * 2012-01-13 2013-07-18 信越石英株式会社 単結晶シリコン引き上げ用シリカ容器及びその製造方法
JP5308594B1 (ja) * 2012-01-13 2013-10-09 信越石英株式会社 単結晶シリコン引き上げ用シリカ容器及びその製造方法
CN103502513A (zh) * 2012-01-13 2014-01-08 信越石英株式会社 单晶硅提拉用二氧化硅容器及其制造方法
KR101524427B1 (ko) * 2012-01-13 2015-05-28 신에쯔 세끼에이 가부시키가이샤 단결정 실리콘 인상용 실리카 용기 및 그 제조 방법
US9376761B2 (en) 2012-01-13 2016-06-28 Shin-Etsu Quartz Products Co., Ltd. Single-crystal silicon pulling silica container and method for producing the same
WO2013171937A1 (ja) * 2012-05-15 2013-11-21 信越石英株式会社 単結晶シリコン引き上げ用シリカ容器及びその製造方法
JP5497247B1 (ja) * 2012-05-15 2014-05-21 信越石英株式会社 単結晶シリコン引き上げ用シリカ容器及びその製造方法
KR101497385B1 (ko) * 2012-05-15 2015-03-03 신에쯔 세끼에이 가부시키가이샤 단결정 실리콘 인상용 실리카 용기 및 그 제조 방법
WO2013171955A1 (ja) * 2012-05-16 2013-11-21 信越石英株式会社 単結晶シリコン引き上げ用シリカ容器及びその製造方法
WO2023204146A1 (ja) * 2022-04-18 2023-10-26 信越石英株式会社 単結晶シリコンインゴット引き上げ用石英ガラスるつぼ

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US8915096B2 (en) 2014-12-23
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US20110114530A1 (en) 2011-05-19

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